Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/42—Structural details
  • G03C8/52—Bases or auxiliary layers; Substances therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/42—Structural details
  • G03C8/50—Peel-apart units, i.e. the image-forming section being separated from the image-receiving section

Definitions

• This invention concerns color diffusion transfer photographic film units. More Particularly, it concerns color diffusion transfer photographic film units which can be processed in a light room and with which, after processing, the unified type film unit is peeled apart and the colored image is viewed without having look to through a support.
• Conventional color diffusion transfer photo­graphic film units can be generally classified as being of the peel-apart type or of the non-peeling type.
• the peel-apart type have the photosensitive layer and the dye image receiving layer coated onto separate supports and, after image exposure, the photosensitive element and the dye receiving element are brought together.
• a processing composition is spread between the elements, and a dye image subsequently transferred into the dye receiving layer is obtained by peeling off the dye image receiving element.
• the dye receiving layer and a silver halide emulsion layer are established by coating between a transparent support and another support.
• the image receiving layer and the silver halide layer are coated on the same transparent support and embodiments in which they are coated on separate supports.
• a white reflecting layer is established between the image receiving layer and the silver halide emulsion layer.
• the dye image which has been transferred to the image receiving layer can be viewed by reflected light by including a white pigment in the processing composition which is spread between the image receiving layer and the silver halide emulsion layer.
• the distinguishing features of the non-peeling type units are that there is no covering with processing fluid of the type which occurs with the peel-apart type; there is none of the inconvenience in handling which accompanies the bringing together of the film sheets. In addition, they are very easy to deal with.
• the colored image is viewed through the transparent support; thus it is virtually impossible to avoid some loss of picture quality compared to that of the peel-­apart type since the color saturation is diminished by surface reflection and the whiteness of the white base is inadequate because of the poor reflectance of the white reflecting layer.
• the prints obtained are excessively thick since the emulsion layer, the pod and the cover sheet etc. remain in place after use.
• a color diffusion transfer photographic film uniut comprising a white support having provided sequentially thereon a photosensitive element containing at least (a) a layer which has a neutralizing function; (b) a dye image receiving layer; (c) a peeling layer and (d) at least one silver halide emulsion layer associated with dye image forming substances, an alkaline processing composition which contains a light shielding agent, and a transparent cover sheet is disclosed in Japanese Patent Application No. 231374/87.
• the support is a white support
• the silver halide emulsion layer is a multi-layer
• the distance (d) over which the dye formed from the dye image forming substances associated with the silver halide emulsion layer closest to the dye image receiving layer diffuses directly is comparatively very short
• the distance (d′) over which the dye formed from the dye image forming substance associated with the silver halide emulsion layer farthest from the dye image receiving layer diffuses directly is comparatively very long.
• the value of the ratio d′/d is large.
• the dyes formed close to the dye image receiving layer form a transfer colored image in a relatively short time while the dyes which are formed farther from the dye image receiving layer need more time to form a transfer colored image.
• the time required for the completion of the image as a whole is increased, causing adverse effect in color balance.
• the delay in image formation and adverse changes in the color balance before and after completion of the picture are of major importance, and improvement therein is greatly desired.
• a first object of this invention is to provide a film unit which can be processed in a light room, which provides the high picture quality obtained with peel-apart type color diffusion transfer units, and which possesses excellent handling properties of a non-­peeling type color diffusion transfer unit.
• a second object of the invention is to provide high quality color diffusion transfer photographs which are not sticky after peeling apart.
• a third object of the invention is to provide a diffusion transfer method of image formation wherein a high quality colored image which is not sticky can be obtained by processing in a light room.
• Yet another object of the invention is to provide a film unit that can be processed in a light room and wherein the picture can be completed quickly.
• a color diffusion transfer photographic film unit conprising a support which has both a light shielding function and a light reflecting function on and/or in the support and which has established sequentially, on the support, a photosensitive element containing (a) a layer which has a neutralizing function, (b) a dye image receiving layer, (c) a peeling layer, and (d) at least one silver halide emulsion layer associated with at least one dye image forming substance, an alkali processing composition which contains a light shielding agent, and a transparent cover sheet, wherein said cover sheet contains a dye trapping layer.
• film unit conprising a support which has both a light shielding function and a light reflecting function on and/or in the support and which has established sequentially, on the support, a photosensitive element containing (a) a layer which has a neutralizing function, (b) a dye image receiving layer, (c) a peeling layer, and (d) at least one silver halide emulsion layer associated with at least
• the preferred embodiment of the present invention comprises a color diffusion transfer photo­graphic film unit having a support which has a light shielding function and a light reflecting function on and/or in the support and which has provided sequentially thereon a photosensitive element containing (a) a layer which has a neutralizing function, (b) a dye image receiving layer, (c) a peeling layer and (d) at least one silver halide emulsion layer associated with dye image forming substances, and a transparent cover sheet which includes a dye trapping layer, and further provided that an alkaline processing composition, which contains a light shielding agent, is spread between the uppermost layer of the photosensitive element and the dye trapping layer of the cover sheet.
• a photosensitive element containing (a) a layer which has a neutralizing function, (b) a dye image receiving layer, (c) a peeling layer and (d) at least one silver halide emulsion layer associated with dye image forming substances, and a transparent cover sheet which includes a dye trapping layer, and further
• the film unit is exposed from the side of the transparent cover sheet which has a dye trapping layer, after which it is treated with a pressing means whereby the alkaline processing composition is spread uniformly within the film unit, and development is started.
• a print which has no used emulsion layer, pod and cover sheet attached i.e., a so-called conventional print, is obtained by peeling the part which contains the support and the dye image receiving layer from the remaining part of the film unit at the position of the peeling layer after processing.
• photosensitive elements which have the aforementioned light shielding function and light reflecting function can be used in this invention.
• the layer which has a light reflecting function is on the opposite side to the silver halide emulsion layer of the dye image receiving layer, and the layer which has a light shielding function is on the opposite side to the silver halide emulsion layer of the layer which has a light reflecting function or between the silver halide emulsion layer and the image receiving layer.
• the distance between the dye image forming substance layer closest to the dye image receiving layer and the dye image receiving layer is not more than 5 ⁇ , and preferably not more than 3 ⁇ . This range allows for the time for the completion of the image to be reduced because the diffusion distance of the dyes formed from the dye image forming substances is shortened.
• d′/d increases as the value of d becomes smaller as a result of a shortening of the distance between the dye image receiving layer and the aforementioned dye image forming layer.
• the dye trapping layer is conceptually similar to the scavenger mordant layer disclosed in JP-A-50-­142233, where the alkali processing composition and the emulsion layer are located on one side and the dye image receiving layer is located on the other side of both the aforementioned layers, and the scavenger mordant layer is located in a timing layer or behind the timing layer for the aforementioned alkali processing composition layer.
• JP-A as used herein means an "unexamined published Japanese patent application”.
• the scavenger mordant layer described in JP-A-50-142233 is distinguished by being located in the timing layer or behind a timing layer for the alkali processing composition layer to scavenge essentially undesirable processing reaction products and excess dye after a prescribed time, preferably after about 20 to 30 seconds. This reduces fluctuations in D max due to the processing temperature and reduces the variation in D max up to about 4 weeks after the completion of processing. Moreover, in cases where a diffusible dye image providing substance, such as an oxychromic developing agent, is used from the start, this has the advantage of reducing excess dye formation in the image receiving layer without retarding the access time.
• a diffusible dye image providing substance such as an oxychromic developing agent
• the scavenger mordant layers described in JP-A-50-142233 are such that, as can be seen from the preferred embodiments, the distance d for the direct diffusion of the dye, formed from the dye image forming substances associated with the silver halide emulsion layer which is closest to the dye image receiving layer, into the dye image receiving layer is comparatively long because of the presence of the titanium oxide layer and the carbon black layer.
• the value of d′/d is smaller than the value of d′/d in this invention. This difference is crucial in the examples of JP-A-50-142233, because a time of about 20 to 30 seconds is required before the appearance of the scavenger function.
• dye diffusion into the image receiving layer is impeded in the absence of such a delay.
• the desired effect is not achieved if a timing layer is used, as is clear from the illustrative examples.
• the dye trapping layers of this invention are characterized in that they are in direct contact with the alkali processing composition which contains a light shielding agent. In this way, the sharpness of the image is increased, the time required to complete the image is shortened, and there is less change in the color balance of the picture. It is thought that such a pronounced effect is achieved without adverse effect because the value of d′/d is comparatively large.
• JP-B-57-58650 color diffusion transfer photographic film units which have two dye image receiv­ing layers or two layers which can be dyed have been disclosed in JP-B-57-58650 and U.S. Patent 3,620,731 as well as in JP-A-50-142233.
• JP-B as used herein means an "examined Japanese patent publication”.
• Color diffusion transfer photographic film units in which layers which can be dyed are established on each of two transparent supports have been disclosed in JP-B­ 57-58650.
• the photosensitive elements disclosed are structurally distinct from that of the present invention.
• no peeling layer is present in the actual preferred embodiment, and white light reflecting layer and a light shielding layer are included between the first layer which can be dyed and the photosensitive silver halide layer with which dye image forming substances are associated which are established on the first support.
• white light reflecting layer and a light shielding layer are included between the first layer which can be dyed and the photosensitive silver halide layer with which dye image forming substances are associated which are established on the first support.
• a white pigment in the alkaline processing composition, both layers which can be dyed can be viewed as reflection prints through the supports.
• the dye trapping layer in this invention is provided on the opposite side of the dye image receiving layer and several dye image forming substances. It is difficult to appreciate color balance of the dye which is trapped by the dye trapping layer as a color image when matched with color balance of the image receiving layer, because the relative location of the dye trapping layer is also provided on the opposite side of each dye image forming substances as a matter of course. That is, the dye trapping layer has no function with respect to the second image receiving layer, unlike the aforementioned patent.
• the dye trapping layer in this invention only provides a very poor image so that a satisfactoy image can be completed in the image receiving layer, which is to say so as to provide an adequate color density, the desired color balance, and an adequately low minimum density and the desired gradation. This layer essentially lacks the function of an image receiving layer but provides unexpected effects such as acceleration of development, shortening of the time required to complete the formation of the image, increase in sharpness and a smaller change in the color balance.
• JP-A-45-24075 U.S. Patent 3,445,2278, British Patent 642,355, and U.S. Patents 3,227,550 and 3,227,552.
• JP-A-45-24075 it is disclosed that an acid neutralizing layer is established between the dye image receiving layer and the support.
• this method is quite different from the dye image forming method used in this present invention; moreover, the picture quality of the prints obtained therefrom is unsatisfactory.
• a black and white developing agent such as pyrazolidinone
• dye providing compounds which release a diffusible dye, or of which the diffusibility of the compound itself is changed by oxidation and reduction is used as an electron transfer agent in combination with dye providing compounds which release a diffusible dye, or of which the diffusibility of the compound itself is changed by oxidation and reduction.
• a color developing agent is used to generate the dyes, whereby pronounced staining occurs as a result of the residual color developing agent in the dye image receiving layer.
• Patents 4,359,518, 3,674,482 and 4,383,022 but not only are these quite different from the present invention in which dye providing compounds are used, but there is no suggestion of a layer which has a neutralizing function. Furthermore, there is no disclosure in these documents concerning processing in a light room.
• a dye image receiving layer is established on a support and a layer which has a neutralizing function is established between this dye image receiving layer and the support. It is possible in this way to prevent both the occurrence of undesirable fogging during image formation and the occurrence of staining and changes in color of the image dyes while the print is being stored.
• a light shielding function is provided on the opposite side of the photosensitive layer to that on which the processing composition is spread, and a light shielding agent is included in the processing composition which is spread over the upper part of the photosensitive layer during processing so that development process can be carried our in daylight.
• the mordants which can be used in the dye image receiving layer can also be used as mordants in the dye trapping layer.
• the mordants which can be used in the dye trapping layer may be the same as, or different from, the mordants which are used in the dye image receiving layer. It is possible to change the picture quality etc. of the color picture in the image receiving layer by adjusting the extent of dye entrapment by means of the mordanting strength.
• the sharing ratio of the dye formed in the dye image forming substance layer into the dye image receiving layer/the dye trapping layer is changed.
• Hydrophilic colloids known in the industry, such as gelatin, poly(vinyl alcohol) and derivatives thereof, polyvinylpyrrolidone, polyacrylamide, etc., can be used as the hydrophilic colloid.
• gelatin poly(vinyl alcohol) and derivatives thereof, polyvinylpyrrolidone, polyacrylamide, etc.
• the use of gelatin is preferred.
• the coated weight of the dye trapping layer can be varied freely, according to the system, but generally the mordant is coated at a concentration of from 0.1 to 10 g/m2, and preferably at a concetration of from 0.2 to 3 g/m2, and the hydrophilic colloid is coated at a concentration of from 0.1 to 10 g/m2, and preferably at a concentration from 0.2 to 3 g/m2.
• the white support in this invention is a support where at least the side upon which the dye image receiving layer is coated is white.
• Any support which has adequate whiteness and smoothness can be used for this purpose.
• polymer film which have been rendered white by the addition of white pigments such as titanium oxide, barium sulfate, zinc oxide etc.
• a particle size of from 0.1 to 5 ⁇ or by forming micro­ voids by stretching for example films and synthetic papers made from polyethyleneterephthalate, polystyrene or polypropylene which have been formed into a film using a conventional method of successive biaxial stretching, or supports obtained by laminating polyethylene, polyethyleneterephthalate, or polypropylene, for example, which contains titanium white, onto both sides of a sheet of paper, are preferred.
• the thickness of the support is from 50 to 350 ⁇ m, preferably from 70 to 210 ⁇ m, and more preferively from 80 to 150 ⁇ m.
• a light shielding layer can be provided in the support as required.
• use can be made of a support obtained by laminating polyethylene which contains a light shielding agent, such as carbon black, on the back of a white support.
• the amount of black pigment added as a light shielding agent may be adjusted according to the sensitivity of the photosensitive material which is being shielded, but an optical density of from 5 to 10 is desirable.
• the dye image receiving layer used in the invention is a layer which contains a mordant in a hydrophilic colloid. This may take the form of a single layer or it may have a multi-layer construction obtained by coating mordants which have different mordanting strengths as a laminate. Such layers have been described, for example, in JP-A-61-252551. The use of polymeric mordants is preferred.
• the polymeric mordants which can be used in the present invention include polymers which contain secondary or tertiary amino groups, polymers which have nitrogen containing heterocyclic portions, and polymers which contain quaternary ammonium cation groups of which the number molecular weight is at least 5,000, and preferably at least 10,000.
• Examples include the vinylpyridine polymers and vinylpridinium cationic polymers described, for example, in U.S. Patents 2,548,564, 2,484,430, 3,148,061 and 3,756,814; the vinylimidazolium cationic polymers described, for example in U.S. Patent 4,124,386; the polymer mordant which can crosslink with gelatin as described, for example, in U.S. Patents 3,625,694, 3,859,096 and 4,128,538, and British Patent 1,277,453; the aqueous sol type mordants described, for example, in U.S.
• mordants which are not prone to migrate from the mordant layer into another layer are preferred.
• the latex dispersion mordants are especially preferable, and those which have a particle size of from 0.01 to 2 ⁇ , and preferably from 0.05 to 0.2 ⁇ , are particularly useful.
• the amount of mordant coated differs according to the type of mordant, the quaternary cation content, the type and amount of dye which is to be mordant, and the type of binder which is used etc., but an amount of from 0.5 to 10 g/m2 is preferred, an amount of from 1.0 to 5.0 g/m2 is more preferred, and an amount of from 2 to 4 g/m2 is particularly preferred.
• Gelatin poly(vinyl alcohol), polyacrylamide, polyvinylpyrrolidone etc. can be used as the hydrophilic colloid which is used in the image receiving layer, but gelatin is preferred.
• the layer(s) which have a neutralizing function which are used in the present invention are layers which contain a sufficient quantity of an acidic substance to neutralize the alkali introduced from the processing composition. They may have a multi-layer structure incorporating a neutralization rate adjusting layer (timing layer) and an adhesion reinforcing layer, as required.
• the preferred acidic substances are substances which have acidic groups having a pKa value less than 9 (or precursor groups which provide such acidic groups on hydrolysis). Preferred substances include higher fatty acids such as oleic acid as disclosed in U.S. Patent 2,983,606; acrylic acid, methacrylic acid or maleic acid polymers and partial esters or acid anhydrides thereof, such as those described in U.S.
• Patent 3,362,819 acrylic acid/acrylate ester copolymers such those described in French Patent No. 2,290,699, and latex type acidic polymers such as those described, for example, in U.S. patent 4,139,383 and Research Disclosure , No. 16102 (1977).
• acidic polymers include copolymers of vinyl monomers such ethylene, vinyl acetate and vinyl methyl ether, with maleic anhydride, and their n-butyl esters, copolymers of butyl acrylate and acrylic acid, and cellulose acetate hydro­genphthalate.
• polymeric acids may be used in the form of mixtures with hydrophilic polymers.
• examples of such polymers include polyacrylamide, poly­methylpyrrolidone, poly(vinyl alcohol) including partially saponified forms thereof, carboxymethyl­cellulose, hydroxymethylcellulose, hydroxyethylcellulose and poly(methyl vinyl ether). Among these, poly(vinyl alcohol) is preferred.
• polymers other than hydrophilic polymers such as cellulose acetate, can be mixed with the aforementioned polymeric acids.
• the amount of polymeric acid coated is varied according to the amount of alkali spread in the photosensitive elements.
• the equivalent ratio of polymeric acid to alkali per unit area is generally from 0.9 to 2.0. If the amount of polymeric acid is too low, this can result in changes in the hue of the transferred dyes and staining of the white background areas while the use of too much polymeric acid can result in changes in hue and other disadvantages such as reduced resistance to light.
• the preferred equivalent ratio is from 1.0 to 1.3.
• the admixture of too little or too much hydrophilic polymer lowers the quality of the photograph.
• the ratio by weight of hydrophilic polymer to polymeric acid is generally from 0.1 to 10, and preferably from 0.3 to 3.0.
• Additives can be included for various purposes in the layers which have a neutralizing function in this invention.
• film hardening agents well known in the industry can be included to harden the layers, and polyhydroxyl compounds, such as polyethyleneglycol, polypropyleneglycol and glycerine, can be added for improving the brittleness of these films.
• Other additives such as antioxidants, fluorescent whiteners, dyes for providing a blueing effect, development inhibitors and precursors thereof, can also be added, as required.
• the timing layers which are used in conjunction with neutralizing layers may consist of polymers which have a low alkali permeability, such as gelatin, poly­(vinyl alcohol), partially acetylated poly(vinyl alcohol), cellulose acetate and partially hydrolyzed poly(vinyl acetate); latex polymers which have been made by copolymerization with small amounts of hydrophilic comonomers such as acrylic acid monomer and which have a high activation energy for alkali permeation; or polymers which have lactone rings.
• polymers which have a low alkali permeability such as gelatin, poly­(vinyl alcohol), partially acetylated poly(vinyl alcohol), cellulose acetate and partially hydrolyzed poly(vinyl acetate); latex polymers which have been made by copolymerization with small amounts of hydrophilic comonomers such as acrylic acid monomer and which have a high activation energy for alkali permeation; or polymers which have lactone rings.
• the timing layers which comprise cellulose acetate as disclosed, for example, in JP-A-54-136328 and U.S. Patents 4,267,262, 4,009,030 and 4,029,849; the latex polymers obtained by copoly­merization with small amount of a hydrophilic comonomer such as acrylic acid as disclosed, for example in JP-A-­54-128335, JP-A-56-69629 and JP-A-57-6843, and U.S. Patents 4,056,394, 4,061,496, 4,199,362, 4,250,243, 4,256,827 and 4,268,640; the polymers which have lactone rings as described in U.S.
• timing layers in which these materials are used can take the form of a single layer, or two or more layers may be used conjointly,
• processing can be carried out in daylight because the photosensitive layer is completely shielded from external light during the development process by the light shielding layer in the photosensitive element and the light shielding properties of the processing fluid which is spread over the photosensitive element during processing.
• a layer which contains a light shielding agent can be established by coating on the back of the support, or between the emulsion layer and the support; alternatively, a layer which contains a light shielding agent may be established within the support. Any material which has a light shielding function can be used as a light shielding agent; the use of carbon black is preferred.
• Any binder in which carbon black can be dispersed can be used as the light shielding agent.
• the use of gelatin is preferred.
• a peeling layer is established between the dye image receiving layer and the emulsion layer associated with the dye image forming substances in this invention, such that the emulsion layer can be peeled away after processing.
• the peeling layer must maintain the adhasion between the image forming layer and the emulsion layer in the unprocessed state and peel-away easily after processing. Examples of materials which can be used for this purpose include those disclosed, for example, in JP-A-47-8237, JP-A-59-220727, JP-A-59-­229555, JP-A-49-4653, U.S.
• Water soluble (or alkali soluble) cellulose derivatives provide one example of such materials.
• use can be made of hydroxyethylcellulose, celluslose acetate phthalate, plasticized methylcellulose, ethylcellulose, cellulose nitrate, or carboxymethylcellulose etc.
• Use can also be made of various natural macromolecular materials such as alginic acid, pectin, gum arabic etc.
• Use can also be made of various modified gelatins, for example acetylated gelatin, phthalated gelatin etc.
• use can be made of water-soluble synthetic polymers such as, for example, poly(vinyl alcohol), polyacrylate, poly(methyl methacrylate), butyl methacrylate or copolymers thereof.
• the peelong layer may take the form of a single layer or it may consist of a plurality of layers as disclosed, for example, in JP-A-59-220727 and JP-A-60-­60642.
• a photosensitive layer consisting of silver halide emulsion layer(s) with which dye image forming substances are associated is established above the aforementioned peeling layer in this invention.
• the structural elements of such a layer are described below.
• the dye image forming substances used in the invention are non-diffusible compounds which release diffusible dyes or dye precursors corresponding to the silver image, or compounds having diffusible properties which change in accordance with the silver image; these compounds have been described in the fourth edition of The Theory of the Photographic Process . These compounds can be represented by the general formula [I] below. DYE-Y [1]
• DYE represents a dye or a dye precursor
• Y represents a component which provides a compound which has different diffusion properties from the compound under alkaline condition.
• the compounds can be broadly classified as negative type compounds which become diffusible in the silver image parts, or as positive type compounds which become diffusible in the non-developed parts, according to the function of Y.
• Y in compounds of the negative-type include those which are destroyed by oxidation as a result of development, and which thereby release a diffusible dye.
• N-substituted sulfamoyl groups having groups derived from aromatic hydrocarbon rings or heterocyclic rings as the N-substituent group, are especially desirable as the Y group of negative-type dye releasing redox compounds. Examples of typical groups for Y are indicated below, but Y is not limited to these groups.
• a diffusible dye is released as a result of spontaneous ring closure under alkaline conditions, but the release of the dye is essentially stopped when oxidation occurs with development.
• Y which have such a function have been disclosed, for example, JP-A-­53-69033, JP-A-54-130927 and U.S. Patents 3,421,964, 4,199,355 and 3,980,479.
• the compound does not release a dye itself, but dye is released when reduction occurs.
• Compounds of this type are used in combination with electron donors, and the diffusible dye can be released in the form of the image by reaction with residual electron donor which has been oxidized in the form of the image by silver development.
• Atomic groups which have a function of this type have been disclosed, for example, in U.S.
• ED compounds Combination with non-diffusible electron donat­ing compounds, commonly known as ED compounds, or precursors thereof is preferred when compounds of this type are being used in the present invention .
• Examples of ED compounds have been disclosed, for example, in U.S. Patents 4,263,393 and 4,278,750, and in JP-A-56-­138736.
• DYE represents a dye or a dye precursor as described earlier.
• yellow dyes have been disclosed in U.S. Patents 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609, 4,139,383, 4,195,992, 4,148,641, 4,148,643 and 4,336,322; JP-A-52-114930, JP-A-56-71072; Research Disclosure 17630 (1978) and Research Disclosure 16475 (1977).
• magenta dyes have been disclosed in U.S. Patents 3,453,107, 3,544,545, 3,932,380, 3,931,144, 3,932,308, 3,954,476, 4,233,237, 4,255,509, 4,250,246, 4,142,891, 4,207,104 and 4,287,292; JP-A-52-106727, JP-­A-53-23628, JP-A-55-36804, JP-A-56-73057, JP-A-56-71060 and JP-A-55-134.
• the silver halide emulsions which are used in the present invention may be negative emulsions in which the latent image is formed principally on the surface of the silver halide grains, or internal latent image type direct positive emulsions in which the latent image is formed in the intereor of the silver halide grains.
• the internal latent image type direct positive emulsions are, for example, so-called “conversion” emulsions which have been made using differences in the solubilities of silver halides, or "core/shell” type emulsion in which at least the photosensitive sites of the internal (core) grains of a silver halide which has been doped with metal ions or chemically sensitized, or both doped with metal ions and chemically sensitized, are covered with an outer mantle (shell) of silver halide.
• conversion emulsions which have been made using differences in the solubilities of silver halides
• core/shell type emulsion in which at least the photosensitive sites of the internal (core) grains of a silver halide which has been doped with metal ions or chemically sensitized, or both doped with metal ions and chemically sensitized, are covered with an outer mantle (shell) of silver halide.
• Nucleating agents which can be used for this purpose include, for example, the hydrazines disclosed in U.S. Patents 2,563,785 and 2,588,982; the hydrazides and hydrazones disclosed in U.S. Patent 3,227,552; the heterocyclic quaternary salt compounds disclosed, for example, in British Patent 1,283,835, JP-A-52-69613, and U.S. Patents 3,615,615, 3,719,494, 3,734,738, 4,094,683 and 4,115,122; the sensitizing dyes which have substituent groups which have a nucleating action within the dye molecule as disclosed in U.S.
• Spectrally sensitizing dyes can be used in combination with these negative type emulsions and internal latent image type direct positive emulsions in this invention. Specific examples have been disclosed, for example, in JP-A-59-180550, JP-A-60-140335, Research Disclosure 17029, and U.S.
• At least two photosensitive layers in which silver halide emulsions, which have been spectrally sensitized with the above mentioned spectrally sensitizing dyes, are combined with the aforementioned dye image forming substances which provide dyes having a selective spectral absorbance in the same wavelength range are required to reproduce natural colors using the subtractive color method.
• the emulsion and the dye image forming substance can be established by coating as separate laminated layers or they can be mixed together and established by coating as a single layer. In cases where, in the coated state, the dye image forming substance has an absorption in the spectrally sensitive region of the emulsion with which it is combined, the two are preferably coated in separate layers.
• the emulsion layer may consist of a plurality of emulsion layers which have different speeds, and optional layers may be established between the emulsion layers and the dye image forming substance layer.
• layers which contain nucleation development accelerating agents as disclosed in JP-A-60-­173541 and separating layers as disclosed in JP-B-60-­15267 may be established in order to increase the colored image density.
• reflecting layers as disclosed in JP-A-60-91354 can be established in order to increase the sensitivity of the photosensitive element.
• the blue sensitive emulsion combination unit, the green sensitive emulsion combination unit and the red sensitive emulsion combination unit are established in this order from the side which is to be exposed to light.
• Optional layers can be established, as required, between each of the emulsion layer units.
• the establishment of intermediate layers is especially desirable for preventing the effect of the development of a certain emulsion layer from having an unwanted effect (such as poor color reproductivity by color mixing) in another emulsion layer unit.
• Intermediate layers which contain non-diffusible reducing agents are preferred in cases where developing agents are used in combination with non-diffusible dye image forming substances in order to prevent the diffusion of the oxidized form of the developing agent.
• Specific examples include non-diffusible hydroquinones sulfonamido phenols and sulfonamido naphthols. Examples have been disclosed in JP-B-50-21249, JP-B-50-23813, JP-­A-49-106329, JP-A-49-129535, U.S.
• Anti-irradiation layers, separating layers and protective layers, etc. can be established by coating, as required, in this invention.
• the processing compositions used in the invention are spread uniformly over the photosensitive element after the photosensitive element has been exposed. Together with the light shielding layer, which has been established on the back of the support or on the opposite side of the photosensitive layer from the processing fluid, they completely shield the photo-­sensitive layer from external light. At the same time, the photosensitive layer is developed by means of the components contained within the composition.
• the composition contains an alkali, a viscosity increasing agent, light shielding agent, developing agent and, moreover, development accelerators and development inhibitors for controlling development, and antioxidants, etc. for preventing the deterioration of the developing agent.
• a light shielding agent is always included in the composition.
• the alkali is one which provides a fluid pH of 12 to 14, and examples include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide), alkali metal phosphates (for example, potassium phosphate), guanidines, and the hydroxides of quaternary amines (for example, tetramethylammonium hydroxide).
• alkali metal hydroxides for example, sodium hydroxide, potassium hydroxide, lithium hydroxide
• alkali metal phosphates for example, potassium phosphate
• guanidines for example, guanidines
• hydroxides of quaternary amines for example, tetramethylammonium hydroxide
• the viscosity increasing agents are required to spread the processing fluid evenly and to maintain the adhesion between the photosensitive layer and cover sheet when the used photosensitive layer is peeled away together with the cover sheet.
• use can be made of poly(vinyl alcohol), hydroxyethylcellulose and alkali metal salts of carboxymethylcellulose. Hydroxy­ ethylcellulose and sodium carboxymethylcellulose are preferred.
• any dyes or pigments or combinations thereof, can be used as the light shielding agent provided that they diffuse into the dye image receiving layer and do not cause staining.
• Carbon black is typical of the materials used for this purpose, but combinations of dyes and titanium white can also be used.
• Temporary light shielding dyes which become colorless a fixed time after processing can also be used as dyes for this purpose.
• the preferred developing agents are any of those which undergo cross oxidation of the dye image forming substance and which cause essentially no staining even when oxidized.
• Developing agents of this type can be used individually or two or more types can be used in combination.
• Precursors of developing agents can also be used. These developing agents may be included in an appropriate layer of the photosensitive element or in the alkaline processing fluid.
• Aminophenols and pyrazolidinones are examples of such compounds, but among these, the use of the pyrazolidinones is preferred because of the lower degree of staining.
• a transparent cover sheet is used for spreading the processing fluid uniformly over the photosensitive element in this invention, and a dye trapping layer is provided as the outermost layer on the side of the cover sheet on which the processing fluid is spread.
• any smooth, transparent support normally used in photographic materials can be used as the cover sheet which is used in the invention.
• Materials such as cellulose acetate, polystyrene, polyethylenetere­phthalate and polycarbonate can be used for this purpose, and they may be provided with an under-layer.
• the cover sheet is peeled away together with the processing fluid and the used photosensitive layer after processing.
• the cover sheet can be provided with a neutralizing function in order to control the supplementary neutralization rate and/or to increase the safety of the waste part.
• a neutralizing function is provided, it is preferably established by coating a layer which has a neutralizing function on the support side of the dye trapping layer.
• filter dyes may be included in the cover sheet to adjust the sensitivity of the photosensitive layer. The filter dyes may be added directly into the cover sheet support, or they can be established by coating a separate layer.
• the film units of this invention can be finished as mono-sheets using masking materials, spacer rails, excess fluid trapping materials, etc. as disclosed in JP-B-48-33697, JP-A-48-43317, JP-A-50-153628, JP-A-52-­11027 and JP-A-56-48629.
• slits as disclosed in Research Disclosure No. 23026 (1983) is especially effective for facilitating peeling after processing.
• the form and depth of the slits is selected in accordance with the properties of the support which is being used.
• the Layers (A) and (B) indicated below were established by coating on one side of a PET support which contained titanium white pigment, after which the layers (1) to (26) indicated below were established sequentially by coating on the other side of the support to provide an image receiving photosensitive sheet (1).
• cover sheets (A) to (F) indicated below were each prepared using a transparent polyethylene tere­phthalate support which had 0.05 g/m2 of a gelatin under-layer and which contained dyes for preventing light piping.
• the aforementioned support was used without further treatment.
• a cover sheet prepared by establishing by coating a layer containing 3 g/m2 of gelatin on the aforementioned support.
• a dye trapping layer containing 1 g/m2 of the polymer latex mordant indicated below and 1 g/m2 of gelatin was established by coating on the aforementioned support.
• a dye trapping layer containing 3 g/m2 of the polymer latex mordant indicated below and 3 g/m2 of gelatin was established by coating on the above-­mentioned support.
• a dye trapping layer containing 1 g/m2 of the polymer latex mordant indicated below and 1 g/m2 of gelatin was established by coating on the above-­mentioned support.
• Cover sheet (F) was prepared by establishing by coating the layers (1) and (2) indicated below on the aforementioned support.
• a trapping mordant layer which contained 2 g/m2 of 55% acetylated acetylcellulose and 1 g/m2 of poly(vinylbenzylammonium chloride) was established by coating on the aforementioned support.
• the layers (1) to (3) indicated below were established by coating on the aforementioned support.
• the aforementioned image receiving photo-­sensitive sheet was exposed through a color test chart and then laminated with aforementioned cover sheets (A) to (G) and the processing fluid described blow was spread to a thickness of 80 ⁇ between the two sheets in each case (the spreading of the fluid was achieved with the assistance of a pressing roller). Processing was carried out at 25°C and the units were peeled apart after processing for 2 minutes 30 seconds or 10 minutes.
• the maximum densities at each peeling time and the ratio (%) of the density observed at 2 minutes 30 seconds to that observed on peeling after 10 minutes were measured, and the results obtained are shown in Table 1.
• the density was measured by TCD of Fuji Photo Film Co., Ltd.
• the transfer density ratio at 2 minutes 30 seconds was also especially good for B, and consequently the tricolor transfer balance held and this was excellent.
• the comparative cover sheets there were marked changes in the color balance from 2 minutes 30 seconds to 10 minutes, causing them to be unsatisfactory for commercial use.
• Example 1 The image receiving photosensitive sheet of Example 1 was exposed through a fine line wedge for the evaluation of sharpness and then processed in the same way as in Example 1 using the cover sheets and processing fluid used in Example 1. The units were peeled apart after 10 minutes.
• An image receiving photosensitive sheet (2) was prepared in the same way as in Example 1 except that the coated weights of various layers in the image receiving photosensitive sheet in Example 1 were increased as indicated below: Layer (12) by 1.3 times Layer (15) by 1.3 times Layer (17) by 1.3 times Layer (18) by 1.5 times Layer (21) by 1.5 times Layer (23) by 1.5 times Layer (34) by 1.7 times
• Example 4 Processing was carried out in the same way as in Example 1 using the image receiving photosensitive sheet, cover sheets and processing fluid used in Example 1, and the image was viewed from the cover sheet side 2 minutes after spreading the processing fluid.
• Table 4 Cover Sheet (A) No image to be seen. (B) A faint image was observed but this faded gradually. (C) A faint image was observed. (D) A faint image was observed. (E) A faint image was observed. (F) Virtually no image to be seen. (G) Virtually no image to be seen. (H) A faint image was observed.
• Example 4 The processed film units (C), (D) and (E) in Example 4 were peeled apart after 60 minutes and washed with water to leave just the dye trapping layer, and the image was observed. The density, however, was very low, there was a yellow balance and it could not be said that color pictures were obtained.
• Table 5 Cover Sheet Transmission Optical Density B G R (C) 0.82 0.49 0.35 (D) 0.98 0.55 0.39 (E) 0.86 0.50 0.37
• Example 6 Image Receiving Photosensitive Sheet Minimum Density B G R (1) This Invention 0.16 0.09 0.18 (3) For Comparison 0.28 0.25 0.42
• the neutralizing function is clearly also essential from the point of view of sharpness.
• Image receiving photosensitive sheets were prepared by changing the support in Example 1.
• the layers (1) to (26) and the layers (A) and (B) used for the image receiving photosensitive sheet (1) were established by coating on a support obtained by providing an under-layer of gelatin on a 135 g/m2 weight paper support which had been laminated with poly­ethylene.
• the layers (A) and (B) and the layers (1) to (4) of the image receiving photosensitive sheet (1), a white reflecting layer (4′) containing 2 g/m2 of gelatin and 18 g/m2 of titanium oxide, and the layers (5) to (26) were established by sequentially coating them on a transparent polyethyleneterephthalate support which had been provided with a gelatin under-layer.

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• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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• 1988
  • 1988-02-03 JP JP2349288A patent/JPH0687162B2/ja not_active Expired - Fee Related
• 1989
  • 1989-02-02 EP EP19890101813 patent/EP0327971B1/de not_active Expired - Lifetime
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